Acyl aryl compounds



Patented Apr. 26, 1938 UNITED STATES ACYL ARYL COMPOUNDS Miles Augustinus Dahlen and Newell Meade Bigelow, Wilmington, and Frithjof Zwilgmeyer, Arden, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 20, 1935, Serial No. 55,411

5 Claims.

This invention relates to the manufacture of new compounds having particular use as intermediates for dyestuffs.

In a recently filed application, Dahlen et al., filed SeptemberZO, 1934, Serial Number 744,786, there was disclosed a new series of dyestuffs which, when applied from a developing bath, gave excellent colors despite the fact that none of the components nor the dy'estufi was substantive.

It is an object of this invention to develop new intermediates applicable to the making of azo dyes. Another object of the invention is to prepare the new compounds by methods which are economically and technically satisfactory. Other objects of the invention will be in part apparent and in part more fully hereinafter set forth.

The objects of the invention are accomplished, generally speaking, by the manufacture of compounds of the following formula, which are to the best of our knowledge and belief new:

)m l onto/conic OHN-Aryk-N in which X is hydrogen or an auxochrome, preferably an n-auxochrome, m is an integer at least 3 less than the number of carbon atoms in Aryl, R1 represents one of a group consisting of hydrogen or carbon of the group consisting of alkyl, aryl, and aralkyl, R2 represents carbon of one of the group consisting of alkyl, aryl, aralkyl, and acyl, and in which R1 and R2 may be carbon atoms of one heterocyclic ring. The auxochromes are divided into two groups of which the first, called n-auxochromes, consisting of the group alkyl, alkoxy, halogen, aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy, and trifluoro alkyl, does not tend to water-solubilize the resulting compound, and of which the second, including the carboxylic, and sulfonic acid groups tends to make the compound water-soluble. The acyl radicals are preferably of the aliphatic, aromatic, hydroaromatic or heterocyclic series. In the preferred form of this invention the aryl nucleus will not contain a water-solubilizing group and it is only in the relatively rare instances when a water-soluble compound is desired that a watersolubilizing radical will be attached to the intermediate.

The new compounds may be prepared by a number of reactions whose nature is understood by persons skilled in organic chemistry. In one of these methods, constituting a preferred process in this instance, an aromatic diamine, one of whose amino groups carries the desired substituents, andthe other of whose amino groups is free to react, is added slowly to hot aceto-aceticester either by itself or mixed with an inert diluent. Condensation takes place with the elimination of ethyl alcohol and the product may be isolated 'by any satisfactory process. In another method a diamine carrying a selected substituent group if desired is -mixed with acetoacetic-ester in the cold and the mixture is rap- EXAMPLE I 2-acetyl-amino-aceto-acetcmilide This reaction was carried out in a vessel equipped with agitation, means for the addition of solids or liquids, a thermometer, and a steamjacketed reflux condenser, by means of which all vapors of high-boiling liquids could be condensed and returned to the system, while the alcohol formed during the course of the reaction was allowed to escape.

Five parts of aceto-acetic-ester were heated to 160 C. To this hot solution one part of orthoamino-acetanilide was added. The temperature of the reaction mixture was brought back to I 150 C. as rapidly as possible, and held at this point for 15 minutes. On cooling, 1 part of 2- acetyl-amino-aceto-acetanilide crystallized from the reaction mixture. After recrystallization from boiling ethyl alcohol, the product melted at 127-129 C. The product hadthe formula;

-NHCOCH2COCH::

NHCOCH3 EXAMPLE II 1 -aoeto-acetyZ-amino-2-acetyZ-amino-- naphthalene A mixture of 60 parts of aceto-acetic-ester and 1 part of pyridine was heated to 150 C. in the apparatus described in the previous example. 8 parts of 1-amino-2-acetyl-amino-naphthalene was added to the mixture, and the temperature of the mixture was brought back to 150 as rapidly as possible. The solution was held at this temperature for 15 minutes. On cooling, ap proximately 6 parts of 1-aceto-acetyl-2-acetylamino-naphthalene crystallized out. fled product melted at 188-190 C., with decomposition. The product had the formula:

NHCOCH3 EXAMPLE III 3-dimethyl-amino-aceto-acetanilide A solution of 50 parts of 3-amino-dimethyl-aniline in parts of xylene was added over the course of 20 minutes to parts of aceto-aceticethyl-ester, the temperature of the reaction mixturebeing held at 150 C'., throughout the addition. When all of the amine had been added, the solution was heated at 150 for 10 minutes more, and was then cooled. The mixture was freed of xylene and excess aceto-acetic-ester by a steam distillation. The residue then was slurried with dilute aqueous sodium-hydroxide for an hour. Upon separation and'acidiflcation of the aqueous phase, a small amount of 3-dimethyl-amino-aceto-acetanilide separated out as a dark viscous oil. The product had the formula:

' NHCOCHzCOCHa EXAMPLE IV 3-methoazy-4-acetyl-amino-aceto -acetanilide DITHC O C1120 0 CH3 00H; tastes.

EXAMPLEV 4-ccetyl-amino-2,5-dimethoiry-acetmacetanilide 1 part of 4-amino-2,5-dimethoxy-acetanilide was added in small portions over the course of one-half hour to a refluxing mixture of 2 parts of aceto-acetic-ester and 2 parts of xylene, to which The puri The was filtered from the reaction mixture.

a small amount of pyridine had been added. After the amine all had been added, the mixture was refluxed for a half hour and then chilled. The crude product was filtered off and subjected to a treatment with alkali,- as described in the previous example. About 1 part of the pure product, melting at 209 -21 0 C., was obtained. The product had the formula:

lTTHC oorno 0011.

NBC 0 0 H3 EXAMPLE VI 3 -methyZ-4-benzog Z- amino-aceto acetanilide 1 part of 3-methyl-4-benzoyl-amino-aniline was added in two equal portions, 15 minutes apart, to a refluxing mixture of two parts of aceto-acetic-ester and 2 parts of xylene. The

solution was refluxed for'10 minutes after the second addition of the amine. uct which separated out on cooling was filtered from the reaction mixture and recrystallized from boiling ethyl alcohol. The yield was roughly 0.8 part of product melting at 150-151 C. The product had the formula:

ITIHC O CHICOCHI NH0 0 CaH EXAMPLE VII 1 part of 4-furoyl-amino-2,5-diethoxy-aniline was added in small portions to three parts of EXAMPLE VIII 4-carbo-methomy-amino-2,5-diethoxy-acetoaoetanilide A mixture of 1 part of 4-carbo-methoxy-amino- 2,5-diethoxy-aniline with 2 parts of aceto-aceticester was heated to 150 C. as rapidly as possible, and held at this temperature for a half hour. The crude product crystallized out on cooling, and The product, after recrystallization from hot xylene, amounted to 50% of the theoretical yield and The crude prodmelted at 187-189" 0. The product had the formula: A a

NBC 0 OHaC O CH:

OCaHs CaHlO NHCOOCH] EXAMPLE IX Aceto-acetyZ-para-phenyl-amino-aniline A solution of 2 parts of para-amino-diphenylamine in 2.5 parts of warm xylene was added over the course of 20 minutes to arefluxing mixture of 1 part of aceto-actic-ester with 1 part of xylene. The heating was continued for 15 minutes, and the reaction mixture was chilled and run into 10 parts of 10% sodium-hydroxide solution. After an hours stirring, the aqueous layer was separated, clarified and neutralized with hydrochloric-acid. After recrystallization from boiling ethyl alcohol the product melted at 88-90" C. The yield was approximately 50% of the theory. The product had the formula:

NHCOCHaCOCH:

EXAMPLE X 4- (4'-ethoa:y-phenyl-amino) -aceto-acetanilide 1 part of 4-amino-4-ethoxy-{diphenylamine, dissolved in 4 parts of hot xylene, was added over the course of a half-hour to 1.5 parts or acetoacetic-ester. The temperature of the reaction mixture was maintained at 150 C. When the addition was complete, the reaction mixture was refluxed for 20 minutes more. The xylene and excess aceto-acetic-ester were removed by a steam distillation. The residue was agitated for an hour with an excess of sodium-hydroxide solution. The crude product was recovered by acidiflcation of the aqueous layer, and was purified by recrystallization from boiling ethyl alcohol. The pure product melted at 122423" C. The product had the formula:

IIIHCOCHICOCHQ Exmrm XI 4-dimethyl-a'mino-aceto-acetanilide A solution of 1 part of paraamino-dimethylaniline in 2 parts of xylene was added slowly to 5 parts of aceto-acetices'ter. The temperature of the reaction mixture was maintainedat 150- C.

during the addition, and for a further period of one-half hour. The crude product, filtered from the cooled reaction mixture, was recrystallized from boiling ethyl alcohol. The pure product melted at 109-111 C. The product had the formula: NHCOOHiCOCHl W Ht): EXAMPLE X II 4-ethyl-benzyl-amino-aceto-acetanilide days standing. After recrystallization from boiling ethyl alcohol, the product melted at 73-76 C. The product had the formula: 1

l inooonloooni Aceto-acetyl-4-(N-methyZ-phenylamino) -amline A solution of 1 part of para-amino-diphenylmethylamine in xylene was added over the course of a half hour to a refluxing solution of 2 parts of aceto-acetic-ester and '2 parts of xylene. The product, isolated by steam distillation, alkaline extraction and reacidification, separated as an oil which could not be recrystallized. The product had'the formula:

III-CH;

EXAMPLE xiv Pam-aceto-acetyb amino-phenyl-morpholine 1 part of para-amino-phenyl-morpholine was added in small installments to a refluxing solution of 2 parts of aceto-acetic-ester and 1.5 parts of xylene over the course of a half hour. On cooling, the crude product separated from the reaction mixture. The crude product was purified by recrystallization from ethyl alcohol. The

.product melted at PIG-147 C., and had the formula:

. llqnooomooom VEXVAMPIE XV 3-chZ0ro-4-acto-acetyZ-dmino-phenylmorpholine '1 part of 3-chloro-4amino-phenyl-'morpholine was added in small installments to 4 parts of aceto-a'cetic-e'ster "at 150 C. The solution was heated in all for 1 hour, and thenwas chilled. The crude product was purified by solution in alkali and recrystallized. The purified product melted at -167 C; The product had the formula:

Nnoocmooom' EXAMPLE XVI 4-aceio-acetyl-dhziizo-Zfi-diethoxy-phenyl morpholine 1 part of 4-amino--2,5-diethoxy-phenyl--morpholine was mixed with '100 g. of aceto-aceticester and heated as rapidly as possible to 150 C. The mixture was held at this temperature for one-half hour, and'then was chilled. The crude product, which crystallized out on cooling, was purified by recrystallization from ethyl alcohol. The product was obtained in 53% yield, and melted at 137-439 C., having the formula:

IIQ'HCOCH2COCH CzHrO (3111 2 CH1 oHli EXAMPLE xvii N 5 (4-aceto-acetyl-a.mino-phenyl) -piper2dz'ne A solution of 1 part of 4-amino-ph-enyl-piperidine in 8 parts of xylene was added over the course of a half hour to 3 parts of aceto-aceticester at 140-150 C. The reaction mixture was refluxed for a further 10 minutes and then was cooled. The crude productwas filtered. off and recrystallized from ethyl alcohol. 'The product their use.

Weighed 36%:of the theory and melted at131f 0., having the formula:

Nnooomooom product weighed 45% of the theory, and melted at 106-108 C. The product had the formula:

CnHnO on, S eal v Gaffe. uj. In .the Inlet nod of ammo-substituted aceto-acetanilide in, which the reaction .is between an ester of aoeto-acetic-acid and anaro- .matic diamine containing one free aminogi oup the yield is better if the amineis addedto'the hot esterin such amanner that an excess of the ester is present, but this condition does:v not uniformly prevail and modificationin the order of the addition ofthe reagents does notalter the principal result. v Catalysts may be usedand in some instances desirable results are obtainedby Many others modificationsv Of .the in Vention will occur; topersons skilledin, the, art

and all such are regarded as within the scopeof the invention. v v

As many apparently Widely different embodiments of the invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodimentstthereof except as defined in the appended claims.

We claim:

1. The product represented by the formula 2. The vmethod which comprisesheating about 5 parts aceto'aceticester to about 160 C., addingthereto: about 1 part ortho-amino-acet-anilide, heating the mixture. at about 150-'C.' for about15 minutes, precipitating the. product gby cooling, and recrystallizing it from ethyl alcohol.

8. The method which comprises heating a mixture containing aceto-acetic-ester and orthoamino-acetanilide at about 150 0., and isolating the product.

4. In the process of making amino-substituted aceto-acetani1ides the step which comprises mixing ortho-amino-acetanilide with hot acetoacetic-ester, and retaining the mixture in a 10 heated condition until an amino-substituted compound is formed which will precipitate upon cool- 5. In the process of making amino-substituted mono-aceto-acetanilides, the step which comprises mixing ortho-amino-acetanilide with hot aceto-acetic-ester, said ester being in excess of an equimolecular proportion.

MILES AUGUSTINUS DAI-ILEN. NEWELL MEADE BIGELOW. FRITHJOF ZWILGMEYER. 

